Renewable compositions

• US 8,546,627 B2
• Filed: 04/06/2012
• Issued: 10/01/2013
• Est. Priority Date: 12/03/2007
• Status: Expired due to Fees

• Current Assignee: Gevo Incorporated
• Original Assignee: Gevo Incorporated
• Inventors: Gruber, Patrick R., Peters, Matthew W., Griffith, Josefa M., Obaidi, Yassin Al, Manzer, Leo E., Taylor, Joshua D., Henton, David E.
• Primary Examiner(s): MCAVOY, ELLEN M
• Application Number:
  US13/441,468
• Publication Number:
  US 20120259146A1
• Time in Patent Office: 543 Days
• Field of Search: 585/240, 585407-421
• US Class Current: 585/240
• CPC Class Codes: C07C 1/24 by elimination of water
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 11/09 Isobutene
• CPC Class Codes: C07C 15/00 Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07C 2/08 Catalytic processes
• CPC Class Codes: C07C 2/76 by condensation of hydrocarbons with partial elimination of hydrogen
• CPC Class Codes: C07C 5/03 of non-aromatic carbon-to-carbon double bonds
• CPC Class Codes: C07C 51/265 having alkyl side chains which are oxidised to carboxyl groups
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid
• CPC Class Codes: C07C 9/14 with five to fifteen carbon atoms
• CPC Class Codes: C07C 9/15 Straight-chain hydrocarbons
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 2400/30 Aromatics
• CPC Class Codes: C10G 3/00 Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids production from non-melting solid oxygen-containing carbonaceous materials C10G1/00
• CPC Class Codes: C10G 50/00 Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10G 69/126 polymerisation, e.g. oligomerisation
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 1/06 : for spark ignition
• CPC Class Codes: C10L 1/08 : for compression ignition
• CPC Class Codes: C10L 2200/043 : Kerosene, jet fuel
• CPC Class Codes: C10L 2200/0469 : Renewables or materials of biological origin
• CPC Class Codes: C10L 2270/04 : for turbines, planes, power generation
• CPC Class Codes: C10L 2290/26 : Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
• CPC Class Codes: C10L 2290/543 : Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
• CPC Class Codes: C12P 5/00 : Preparation of hydrocarbons or halogenated hydrocarbons
• CPC Class Codes: C12P 7/04 : acyclic
• CPC Class Codes: C12P 7/06 : Ethanol, i.e. non-beverage
• CPC Class Codes: C12P 7/16 : Butanols
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock
• CPC Class Codes: Y02T 50/678 : Aviation using fuels of non-fossil origin

Abstract

The present invention is directed to renewable compositions derived from fermentation of biomass, and integrated methods of preparing such compositions.

Claims

1. A process for preparing a renewable jet fuel comprising:

(a) treating biomass to form a feedstock;

(b) fermenting the feedstock with one or more species of microorganism, thereby forming one or more C₂-C₆ alcohols;

(c) dehydrating at least a portion of the one or more C₂-C₆ alcohols obtained in step (b), thereby forming a product comprising one or more C₂-C₆ olefins;

(d) isolating the one or more C₂-C₆ olefins;

(e) oligomerizing at least a portion of the one or more C₂-C₆ olefins isolated in step

(d), thereby forming a product comprising one or more C₆-C₂₄ unsaturated oligomers;

(f) optionally hydrogenating at least a portion of the product of step (e) in the presence of hydrogen, thereby forming a product comprising one or more C₆-C₂₄ saturated alkanes; and

(g) combining the product of step (f) with one or more C₁₀-C₁₄ aromatic hydrocarbons, thereby forming a jet fuel;

whereby the product of step (g) meets the requirements of ASTM D1655.

2. The process of claim 1, wherein said dehydrating, oligomerizing, and hydrogenating are each carried out in the presence of a dehydration catalyst, oligomerization catalyst, and a hydrogenation catalyst, respectively.

3. The process of claim 2, wherein each of said dehydrating, oligomerizing, and hydrogenating are carried out in a different reaction zone.

4. The process of claim 2, wherein two or more of said dehydrating, oligomerizing, and hydrogenating are carried out in the same reaction zone.

5. The process of claim 2, wherein one or more of the dehydration catalyst, oligomerization catalyst, or hydrogenation catalyst are heterogeneous catalysts.

6. The process of claim 2, wherein one or more of the dehydration catalyst, oligomerization catalyst, or hydrogenation catalyst are homogeneous catalysts.

7. The process of claim 1, wherein said dehydrating and/or said oligomerizing are carried out in the presence of an acidic catalyst, wherein the acidic catalyst for dehydrating and the acidic catalyst for oligomerizing is the same or different.

8. The process of claim 1, wherein said C₁₀-C₁₄ aromatic hydrocarbons are prepared by:

(1) aromatizing one or more C₂-C₆ olefins, one or more dimers of C₂-C₆ olefins, and/or one or more trimers of C₂-C₆ olefins; and

optionally

(2) oligomerizing the product of step (1).

9. The process of claim 8, wherein the one or more C₂-C₆ olefins are obtained from step (d) and the dimers and trimers of C₂-C₆ olefins are obtained from step (e).

10. The process of claim 8, wherein at least a portion of the hydrogen used in step (f) is provided by hydrogen formed as a byproduct of step (1).

11. A renewable jet fuel prepared by the process of claim 1.

12. A renewable jet fuel prepared by the process of claim 8.

13. A renewable jet fuel prepared by the process of claim 10.

14. The process of claim 1, further comprising removing said C₂-C₆ alcohols from the feedstock before said dehydrating.

15. The process of claim 14, wherein said removing comprises carrying out said fermenting in step (b) below atmospheric pressure, whereby aqueous C₂-C₆ alcohol vapor is removed.

16. A process for preparing a renewable aromatic compound, comprising:

(i) treating biomass to form a feedstock;

(ii) fermenting the feedstock with one or more species of microorganism, thereby forming one or more C₂-C₆ alcohols;

(iii) dehydrating at least a portion of the one or more C₂-C₆ alcohols obtained in step (ii), thereby forming a product comprising one or more C₂-C₆ olefins;

(iv) isolating the one or more C₂-C₆ olefins;

(v) optionally oligomerizing the one or more C₂-C₆ olefins to one or more dimers and/or one or more trimers of the C₂-C₆ olefins;

(vi) aromatizing one or more C₂-C₆ olefins from step (iv) or one or more dimers and/or one or more trimers of the C₂-C₆ olefins of step (v), thereby forming a product comprising C₆-C₁₄ aromatic hydrocarbons, and hydrogen; and

(vii) optionally oligomerizing the product of step (vi) in the presence of the one or more C₂-C₆ olefins of step (v) to form a product comprising one or more C₈-C₁₆ aromatic hydrocarbons.

17. A process of preparing renewable terephthalates, comprising preparing renewable p-xylene by the method of claim 16, wherein the product of step (vi) comprises at least 50% p-xylene, and further comprising:

(a) optionally isolating and purifying the p-xylene of step (vi); and

(b) oxidizing the p-xylene, optionally in the presence of one or more alcohols, thereby forming renewable terephthalates.

18. A renewable jet fuel or jet fuel precursor comprising a mixture of aromatic hydrocarbons and C₁₁-C₁₄ aliphatic hydrocarbons.

19. The renewable jet fuel of claim 18, comprising:

about 65 vol. % to about 85 vol. % of one or more C₁₁-C₁₄ aliphatic hydrocarbons; and

about 10 vol. % to about 20 vol. % of aromatic hydrocarbons.

20. The renewable jet fuel of claim 18, wherein the one or more C₁₁-C₁₄ aliphatic hydrocarbons comprise one or more pentamethylheptane isomers.

21. The renewable jet fuel of claim 18, wherein the one or more C₁₁-C₁₄ aliphatic hydrocarbons comprise one or more hydrocarbons selected from the group consisting of trimethylpentanes, pentamethylheptanes, tetramethyloctanes, heptamethylnonanes, trimethylnonanes, and combinations thereof;

and the alkylated aromatic hydrocarbons comprise one or more mono- or dialkyl benzenes.